Details

Autor(en) / Beteiligte

• Baeza Cinco, Miguel Á.
• Chakraborty, Arunavo
• Guzman, Camilo F.
• Kräh, Sabrina
• Wu, Guang
• Hayton, Trevor W.

Titel

NO and N2O Release from the Trityl Diazeniumdiolate Complexes [M(O2N2CPh3)3]− (M = Fe, Co)

Ist Teil von

• Inorganic chemistry, 2023-03, Vol.62 (12), p.4847-4852

Ort / Verlag

American Chemical Society

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Reaction of MBr2 with 3 equiv of [K­(18-crown-6)]­[O2N2CPh3] generates the trityl diazeniumdiolate complexes [K­(18-crown-6)]­[M­(O2N2CPh3)3] (M = Co, 2; Fe, 3) in good yields. Irradiation of 2 and 3 using 371 nm light led to NO formation in 10 and 1% yields (calculated assuming a maximum of 6 equiv of NO produced per complex), respectively. N2O was also formed during the photolysis of 2, in 63% yield, whereas photolysis of 3 led to the formation of N2O, as well as Ph3CN­(H)­OCPh3, in 37 and 5% yields, respectively. These products are indicative of diazeniumdiolate fragmentation via both C–N and N–N bond cleavage pathways. In contrast, oxidation of complexes 2 and 3 with 1.2 equiv of [Ag­(MeCN)4]­[PF6] led to N2O formation but no NO formation, suggesting that diazeniumdiolate fragmentation occurs exclusively via C–N bond cleavage under these conditions. While the photolytic yields of NO are modest, they represent a 10- to 100-fold increase compared to the previously reported Zn congener, suggesting that the presence of a redox-active metal center favors NO formation upon trityl diazeniumdiolate fragmentation.